EP0007210B1 - Esterderivate von N-Trifluoracetyl-N-Phosphonmethylglyzin und deren Verwendung als Herbizide - Google Patents

Esterderivate von N-Trifluoracetyl-N-Phosphonmethylglyzin und deren Verwendung als Herbizide Download PDF

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Publication number
EP0007210B1
EP0007210B1 EP79301306A EP79301306A EP0007210B1 EP 0007210 B1 EP0007210 B1 EP 0007210B1 EP 79301306 A EP79301306 A EP 79301306A EP 79301306 A EP79301306 A EP 79301306A EP 0007210 B1 EP0007210 B1 EP 0007210B1
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EP
European Patent Office
Prior art keywords
phenyl
trifluoroacetyl
glycinate
group
ethyl
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Expired
Application number
EP79301306A
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English (en)
French (fr)
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EP0007210A3 (en
EP0007210A2 (de
Inventor
John Edward Franz
Robert John Kaufman
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Monsanto Co
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Monsanto Co
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Publication of EP0007210A3 publication Critical patent/EP0007210A3/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4087—Esters with arylalkanols
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4078—Esters with unsaturated acyclic alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4084—Esters with hydroxyaryl compounds

Definitions

  • This invention relates to ester derivatives of N-trifluoroacetyl-N-phosphonomethylglycine, to herbicidal compositions containing same and to herbicidal methods. More particularly, this invention relates to ester derivatives of N-trifluoroacetyl-N-phosphonomethylglycine wherein the groups bonded to the phosphorus atom are different than the group attached to the carboxyl group.
  • N-perfluoroacyl-N-phosphonomethylglycines of the formula wherein n is an integer of from 1 to 4 and m is 1 or 0 are produced by reacting a perfluoroacyl anhydride with N-phonomethylglycine in the presence of a perfluoroalkanoic acid to form the compound of the formula wherein m is 1 and then by hydrolysis to form the compounds wherein m is 0.
  • N-phosphonomethylglycine its salts, amides, esters and other derivatives are disclosed in U.S. Patent No. 3,799,758 and are' shown to be post-emergent herbicides.
  • Other derivatives of N-phosphonomethylglycine and the plant growth regulation use thereof are disclosed in U.S. Patent No. 3,853,530.
  • the production of triesters of N-phosphonomethylglycine is disclosed in U.S. Patent Nos. 4,053,505 and 3,835,000 and in Belgian Patent 849,907.
  • novel N-trifluoroacetyl-N-phosphonomethylglycine esters of this invention are those mixed ester derivatives having the formula wherein R is an alkyl group containing 1 to 10 carbon atoms or a phenyl group and R' is a member of the group consisting of allyl, naphthyl, benzyl and ring-substituted benzyl wherein the substituent is halo, cyano, nitro and trifluoromethyl, phenyl and phenyl substituted with one or two groups selected from the class consisting of halo, cyano, nitro and trifluoromethyl.
  • One aspect of the present invention is a herbicidal method which comprises contacting the plant or plant growth medium with a herbicidally effective amount of a compound of the formula wherein R is an alkyl group containing from 1 to 10 carbon atoms or a phenyl group and R' is a member of the group consisting of allyl, naphthyl, benzyl and ring-substituted benzyl wherein the substituent is halo, cyano, nitro or trifluoromethyl, phenyl and phenyl containing one or two groups selected from the class consisting of halo, cyano, nitro and trifluoromethyl.
  • Another aspect of the present invention is a herbicidal composition characterized in that it contains an inert adjuvant and a compound of the formula wherein R is alkyl group containing from 1 to 10 carbon atoms or a phenyl group and R' is a member of the group consisting of allyl, naphthyl, benzyl and ring-substituted benzyl wherein the substituent is halo, cyano, nitro or trifluoromethyl, phenyl and phenyl containing one or two groups selected from the class consisting of halo, cyano, nitro and trifluoromethyl.
  • halo includes chloro, bromo, iodo and fluoro.
  • halo groups are chloro or fluoro.
  • R' represents are monosubstituted phenyl groups wherein the substituent is in the ortho, meta or para position, for example, chlorophenyl, broniophenyl, fluorophenyl, cyanophenyl, nitrophenyl and trifluorophenyl and the disubstituted phenyl groups wherein the substituents are the same or different and are located in the 2, 3, 4, 5 or 6 positions of the phenyl group, for example, dichlorophenyl, dibromophenyl, chlorocyanophenyl, dicyanophenyl, dinitrophenyl, bromonitrophenyl, chlorotrifluoromethylphenyl and the like.
  • the ring-substituted benzyl groups include benzyl groups containing the substituents set forth above for the substituted phenyl groups.
  • R is a lower alkyl group, i.e., an alkyl group containing from 1 to 4 carbon atoms.
  • novel compounds of this invention are produced by reacting an ester dichloride of N-trifluoroacetyl-N-phosphonomethylglycine having the formula wherein R is as above defined with a hydroxy compound having the formula wherein R' is as above-defined in an organic solvent and in the presence of a tertiary amine hydrogen chloride acceptor under essentially anhydrous conditions at a temperature of from about 10°C. to about 50°C. preferably at ambient temperatures.
  • tertiary amine hydrogen chloride acceptor is preferably used in excess of stoichiometric to insure completeness of reaction.
  • tertiary amine hydrogen chloride acceptor as employed herein is meant tertiary alkylamines such as trimethylamine, triethylamine, tributylamine, trihexylamine and the like as well as aromatic tertiary amines such as pyridine, quinoline and the like.
  • the ratio of the reactants can vary over wide ranges. It is, of course, apparent to those skilled in the art that each chlorine atom in the N-trifluoroacetyl-N-phosphonomethylglycinyl dichloride will react with one alcohol group (R'-O-H) and that, therefore, one would employ the reactants in equivalent amounts. When employing an alcohol which is volatile, it is sometimes desirable to employ an excess of the alcohol. In other instances such with the phenols, it is sometimes preferred to use a slight excess of the glycinyl dichloride for ease of recovery of the product.
  • the ester dichlorides of Formula II employed as a reactant in producing the compounds of this invention are prepared by reacting an ester of N-phosphonomethylglycine of the formula _ wherein R has the above defined meaning with trifluoroacetic acid anhydride at temperatures of from about 10°C. to about 35°C., removing any excess anhydride and then treating the reaction product with excess thionyl chloride under refluxing conditions. The excess thionyl chloride is removed under vacuum to yield the dichlorides of Formula II.
  • the compounds of this invention are useful as herbicides.
  • the post-emergence herbicidal activity of the various compounds of this invention is demonstrated by greenhouse testing in the following manner.
  • a good grade of top soil is placed in aluminum pans having holes in the bottom and compacted to a depth of .95 to 1.27 cm. from the top of the pan.
  • a predetermined number of seeds of each of several dicotyledonous and monocotyledonous annual plant species and/or vegetative propagules for the perennial plant species are placed on the soil and pressed into the soil surface. The seeds and/or vegetative propagules are covered with soil and leveled.
  • the pans are then placed on a sand bench in the greenhouse and watered from below as needed.
  • each pan except for the control pans is removed individually to a spraying chamber and sprayed by means of an atomizer operating at a positive air pressure of approximately 1.46 kg/cm 2 absolute.
  • the atomizer contains 6 ml. of a solution or suspension of the chemical and an amount of a cyclohexanone emulsifying agent mixture so that the spray solution or suspension contains about 0.4% by weight of the emulsifier.
  • the spray solution or suspension contains a sufficient amount of the candidate chemical in order to give application rates corresponding to those set forth in the tables.
  • the spray solution is prepared by taking an aliquot of a 1.0% by weight stock solution or suspension of the candidate chemical in an organic solvent such as acetone or tetrahydrofuran or in water.
  • the emulsifying agent employed is a mixture comprising 35 weight percent butylamine dodecylbenzene sulfonate and 65 weight percent of a tall oil ethylene oxide condensate having about 11 moles of ethylene oxide per mole of tall oil.
  • the pans are returned to the greenhouse and watered as before and the injury to the plants as compared to the control is observed at approximately two and four weeks as indicated in the tables under WAT and the results recorded. In some instances, the four-week observations are omitted.
  • the post-emergence herbicidal activity index used in Tables I and II is as follows:
  • the pre-emergent herbicidal activity of various compounds of this invention is demonstrated as follows.
  • a good grade of top soil is placed in aluminum pans and compacted to a depth of .95 to 1.27 cm. from the top of each pan.
  • a predetermined number of seeds or vegetative propagules of each of several plant species are placed on top of the soil in each pan and then pressed down.
  • Herbicidal compositions prepared as in the previous example are applied by admixture with or incorporation in the top layer of soil.
  • the soil required to cover the seeds and propagules is weighed and admixed with a herbicidal composition containing a known amount of the active ingredient (compound of this invention).
  • the pans are then filled with the admixture and leveled. Watering is carried out by permitting the soil in the pans to absorb moisture through apertures in the pan bottoms.
  • the seed and propagule containing pans are placed on a wet sand bench and maintained for approximately two weeks under ordinary conditions of sunlight and watering. At the end of this period, the number of emerged plants of each species is noted and compared to an untreated control.
  • the data is given in the following table.
  • the pre-emergent herbicidal activity index used below is based upon average percent control of each species as follows:
  • Plant species in the table are identified by the same code letters used in the previous example.
  • the herbicidal compositions including concentrates which require dilution prior to application to the plants, of this invention contain from 5 to 95 parts by weight of at least one compound of this invention and from 5 to 95 parts by weight of an adjuvant in liquid or solid form, for example, from about 0.25 to 25 parts by weight of wetting agent, from about 0.25 to 25 parts by weight of a dispersant and from 4.5 to about 94.5 parts by weight of inert liquid extender, e.g., water, acetone, tetrahydrofuran, all parts being by weight of the total composition.
  • the compositions of this invention contain from 5 to 75 parts by weight together with the adjuvants.
  • compositions are prepared by admixing the active ingredient with an adjuvant including diluents, extenders, carriers and conditioning agents to provide compositions in the form of finely-divided particulate solids, pellets, solutions, dispersions or emulsions.
  • an adjuvant such as a finely-divided solid, a liquid of organic origin, water, a wetting agent, a dispersing agent, an emulsifying agent or any suitable combination of these.
  • compositions of this invention preferably contain as a conditioning agent one or more surface-active agents in amounts sufficient to render a given composition readily dispersible in water or in oil.
  • a surface-active agent it is understood that wetting agents, dispersing agents, suspending agents and emulsifying agents are included therein.
  • Anionic, cationic and nonionic agents can be used with equal facility.
  • Preferred wetting agents are alkyl benzene and alkyl naphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters petroleum sulfonates, sulfonated vegetable oils, polyoxyethylene derivatives of phenols and alkylphenols (particularly isooctylphenol and nonylphenol) and polyoxyethylene derivatives of the mono-higher fatty acid esters of hexitol anhydrides (e.g., sorbitan).
  • Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin, sulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalene sulfonate, polymethylene bisnaphthalene- sulfonate and sodium N-methyl-N-(long chain acid) taurates.
  • effective amounts of the compound or compositions of this invention are applied to the plants, or to soil containing the plants, or are incorporated into aquatic media in any convenient fashion.
  • the application of liquid and particulate solid compositions to plants or soil can be carried out by conventional methods, e.g., power dusters, boom and hand sprayers and spray dusters.
  • the compositions can also be applied from airplanes as a dust or a spray because of their effectiveness at low dosages.
  • the application of herbicidal compositions to aquatic plants is usually carried out by adding the compositions to the aquatic media in the area where control of the aquatic plants is desired.
  • an effective amount of the compound or compositions of this invention to the plant is essential and critical for the practice of the present invention.
  • the exact amount of active ingredient to be employed is dependent upon the response desired in the plant as well as such other factors at the plant species and stage of development thereof, and the amount of rainfall as well as the specific glycine employed.
  • the active ingredients are applied in amounts from about 0.112 to about 22.4 or more kilograms per hectare.
  • the rate of application can be from about 0.56 to about 22.4 or more kilograms per hectare.
  • the active ingredients are applied in amounts of from about 0.01 parts per million to about 1000 parts per million, based on the aquatic medium.
  • An effective amount for phytotoxic or herbicidal control is that amount necessary for overall or selective control, i.e., a phytotoxic or herbicidal amount. It is believed that one skilled in the art can readily determine from the teachings of this specification, including examples, the approximate application rate.

Claims (15)

1. Verbindung, gekennzeichnet durch die Formel
Figure imgb0030
in der R eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen oder eine Phenylgruppe und R' Allyl, Naphthyl, Benzyl, durch Halogen, Cyano, Nitro oder Trifluormethyl ring-substituiertes Benzyl, Phenyl und/ oder ein oder zwei Halogen-, Cyano-, Nitro- und Trifluormethylgruppen enthaltendes Phenyl bedeuten.
2. Verbindung nach Anspruch 1, dadurch gekennzeichnet, daß R' Phenyl oder durch eine oder zwei Halogen-, Cyano-, Nitro- und Trifluormethylgruppen substituiertes Phenyl Bedeutet.
3. Verbindung nach Anspruch 2, dadurch gekennzeichnet, daß R eine niedrige Alkylgruppe ist.
4. Verbindung nach Anspruch 1, dadurch gekennzeichnet, daß R eine niedrige Alkylgruppe und R' eine Naphthylgruppe ist.
5. Verbindung nach Anspruch 3, die Äthyl-N-trifluoracetyl-N-(diphenoxyphosphonomethyl)-glycinat, Äthyl-N-trifluoracetyl-N-(bis(m-nitrophenoxy)phosphonomethyl)glycinat oder Äthyl-N-trifluoracetyl-N-(dinaphthyloxyphosphonomethyl)glycinat ist.
6. Herbizide Zubereitung, dadurch gekennzeichnet, daß sie eine inertes Adjuvans und eine Verbindung der Formel
Figure imgb0031
in der R eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen oder eine Phenylgruppe und R' Allyl, Naphthyl, Benzyl, durch Halogen, Cyano, Nitro oder Trifluormethyl ring-substituiertes Benzyl, Phenyl und/ oder ein oder zwei Halogen-, Cyano-, Nitro- und Trifluormethylgruppen enthaltendes Phenyl bedeuten.
7. Verbindung nach Anspruch 6, dadurch gekennzeichnet, daß R' Phenyl oder durch eine oder zwei Halogen-, Cyano-, Nitro- und Trifluormethylgruppen substituiertes Phenyl bedeutet.
8. Herbizide Zubereitung nach Anspruch 7, dadurch gekennzeichnet, daß R eine niedrige Alkylgruppe ist.
9. Herbizide Zubereitung nach Anspruch 6, dadurch gekennzeichnet, daß R eine niedrige Alkylgruppe und R' eine Naphthylgruppe ist.
10. Herbizide Zubereitung nach Anspruch 6, dadurch gekennzeichnet, daß die Verbindung Äthyl-N-trifluoracetyl-N-(diphenoxyphosphonomethyl)glycinat, Äthyl-N-trifluoracetyl-N-(bis(m-nitrophenoxy)-phosphonomethyl)glycinat oder Äthyl-N-trifluoracetyl-N-(dinaphthyloxyphosphonomethyl)glycinat ist.
11. Herbizides Verfahren, bei dem man die Pflanze oder das Wachstumsmedium einer Pflanze mit einer herbizid wirksamen Menge einer Verbindung in Kontakt bringt, dadurchgekennceichnet, daß die Verbindung der Formel
Figure imgb0032
in der R eine Alkylgruppe mit 1 bis 10 Kohlenstoffatomen oder eine Phenylgruppe und R' Allyl, Naph- thyl, Benzyl, durch Halogen, Cyano, Nitro oder Trifluoromethyl ringsubstituiertes Benzyl, Phenyl und/oder zwei Halogen-, Cyano-, Nitro- und Trifluormethylgruppen enthaltendes Phenyl bedeuten.
12. Herbizides Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß R' Phenyl oder durch eine oder zwei Halogen-, Cyano-, Nitro- und Trifluormethylgruppen substituiertes Phenyl bedeutet.
13. Herbizides Verfahren nach Anspruch 12, dadurch, gekennzeichnet, daß R eine niedere Alkylgruppe ist.
14. Herbizides Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß R eine niedrige Alkylgruppe und R' eine Naphthylgruppe ist.
15. Herbizides Verfahren nach Anspruch 11, dadurch gekennzeichnet, daß die Verbindung Äthyl-N-trifluoracetyl-N-(diphenoxyphosphonomethyl)glycinat, Äthyl-N-trifluoracetyl-N-(bis(m-nitrophenoxy)-phosphonomethyl)glycinat oder Äthyl-N-trifluoracetyl-N-(dinaphthyloxyphosphonomethyl)glycinat ist.
EP79301306A 1978-07-10 1979-07-06 Esterderivate von N-Trifluoracetyl-N-Phosphonmethylglyzin und deren Verwendung als Herbizide Expired EP0007210B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US05/922,920 US4218235A (en) 1978-07-10 1978-07-10 Ester derivatives of n-trifluoroacetyl-n-phosphonomethylglycine and the herbicidal use thereof
US922920 1997-09-03

Publications (3)

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EP0007210A2 EP0007210A2 (de) 1980-01-23
EP0007210A3 EP0007210A3 (en) 1980-02-20
EP0007210B1 true EP0007210B1 (de) 1982-06-02

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US (1) US4218235A (de)
EP (1) EP0007210B1 (de)
JP (1) JPS5513292A (de)
AR (1) AR226287A1 (de)
AU (1) AU520849B2 (de)
BG (1) BG29425A3 (de)
BR (1) BR7904359A (de)
CA (1) CA1131654A (de)
CS (1) CS208122B2 (de)
DD (1) DD144711A5 (de)
DE (1) DE2963001D1 (de)
DK (1) DK148325C (de)
HU (1) HU185007B (de)
IL (1) IL57750A (de)
MX (1) MX5593E (de)
PH (1) PH14396A (de)
PL (1) PL117606B1 (de)
RO (2) RO84199B (de)
ZA (1) ZA793416B (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4444580A (en) * 1982-11-01 1984-04-24 Monsanto Company N-Substituted N-(phosphonomethyl)aminoethanal derivatives as herbicides
US4444581A (en) * 1982-12-13 1984-04-24 Monsanto Company Enamine derivatives of phosphonic acid esters as herbicides
US4569802A (en) * 1983-06-27 1986-02-11 Stauffer Chemical Company Method for preparation of N-phosphonomethylglycine
US4654072A (en) * 1985-09-17 1987-03-31 Stauffer Chemical Company Herbicidal phosphonomethyl amides

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3819353A (en) * 1968-05-24 1974-06-25 Du Pont Plant growth regulant carbamoylphosphonates
PH16509A (en) * 1971-03-10 1983-11-08 Monsanto Co N-phosphonomethylglycine phytotoxicant composition
US3853530A (en) * 1971-03-10 1974-12-10 Monsanto Co Regulating plants with n-phosphonomethylglycine and derivatives thereof
US3799758A (en) * 1971-08-09 1974-03-26 Monsanto Co N-phosphonomethyl-glycine phytotoxicant compositions
US3835000A (en) * 1972-12-21 1974-09-10 Monsanto Co Electrolytic process for producing n-phosphonomethyl glycine
US3970695A (en) * 1975-05-23 1976-07-20 Monsanto Company N-(perfluoroacyl)-N-phosphonomethyl glycine compounds, method of preparing same
US4108626A (en) * 1975-09-25 1978-08-22 E. I. Du Pont De Nemours And Company Alkoxycarbonylphosphonic acid derivative brush control agents
MX3898E (es) * 1975-12-29 1981-09-10 Monsanto Co Procedimiento mejorado para la preparacion de triesteres de n-fosfonometilglicina
US4053505A (en) * 1976-01-05 1977-10-11 Monsanto Company Preparation of n-phosphonomethyl glycine
US4067719A (en) * 1976-12-13 1978-01-10 Monsanto Company O-Aryl N-phosphonomethylglycinonitriles and the herbicidal use thereof

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ZA793416B (en) 1980-07-30
US4218235A (en) 1980-08-19
HU185007B (en) 1984-11-28
IL57750A0 (en) 1979-11-30
DK287679A (da) 1980-01-11
MX5593E (es) 1983-11-03
DD144711A5 (de) 1980-11-05
DK148325C (da) 1985-11-04
DE2963001D1 (en) 1982-07-22
IL57750A (en) 1983-02-23
CS208122B2 (en) 1981-08-31
RO84199B (ro) 1984-08-30
AU520849B2 (en) 1982-03-04
EP0007210A3 (en) 1980-02-20
RO84199A (ro) 1984-06-21
EP0007210A2 (de) 1980-01-23
RO78802A (ro) 1982-04-12
AR226287A1 (es) 1982-06-30
PL117606B1 (en) 1981-08-31
PH14396A (en) 1981-06-25
AU4877379A (en) 1980-01-17
DK148325B (da) 1985-06-10
JPS5513292A (en) 1980-01-30
BR7904359A (pt) 1980-04-08
BG29425A3 (en) 1980-11-14
CA1131654A (en) 1982-09-14
PL216974A1 (de) 1980-06-16

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